64
M. Sha et al. / Journal of Fluorine Chemistry 169 (2015) 61–65
3: white solid, 2.253 g (99% yield); 1H NMR (DMSO-d6, 300 MHz)
: 3.82 (s, CH2, 2H), 7.45 (d, J = 7.8 Hz, Ar-H, 2H), 7.92 (d, J = 7.8 Hz,
Ar-H, 2H); 19F NMR (DMSO-d6, 282 MHz)
6F), ꢁ80.04 (t, J = 13.1 Hz, 3F), ꢁ106.00 to ꢁ106.30 (m, 2F), ꢁ122.90
to ꢁ123.20 (m, 2F); LRMS (EI) m/z (%): 135 (100), 454 (4.7).
Again the MeOH solution was filtered and the filtrate was
concentrated in vacuo leaving a white solid. The solid was washed
with acetone and dried giving a white powder.
d
d: ꢁ61.95 to ꢁ62.20 (m,
6: white powder, 1.024 g (79% yield). 1H NMR (CD3OD,
300 MHz)
d: 3.20 (s, N(CH3)2, 12H), 3.61 (t, J = 6.5 Hz,
CONHCH2CH2, 4H), 3.77 (s, (CH3)2NCH2C6H4, 4H), 3.98 (m,
CONHCH2CH2, 4H), 4.71 (s, C6H4CH2C6F13, 4H), 7.49 (d, J = 8.1 Hz,
Ar-H, 4H), 7.75 (d, J = 8.1 Hz, Ar-H, 4H), 7.81–7.91 (m,
4.2.4. Synthesis of N-(2-dimethylamino-ethyl)-4-(3,3,4,4,5,5,5-
heptafluoro-2,2-bis-trifluoromethyl -pentyl)-benzamide (4)
Acid
3
(5.000 g, 11.0 mmol, 1.0 equiv), DMAP (0.135 g,
CH2C6H4C6H4CH2, 8H); 19F NMR (CD3OD, 282 MHz)
d: ꢁ63.60 to
1.1 mmol, 0.1 equiv) and 1-ethyl-3-(3-dimethyllaminopropyl)car-
bodiimide hydrochloride (EDCI, 3.150 g, 16.5 mmol, 1.5 equiv) were
combined and cooled to 0 8C. Dry CH2Cl2 (50.0 mL) was added and
stirred for 10 min. N,N-dimethylethylene diamine (1.8 mL,
16.5 mmol, 1.5 equiv) was then added dropwise with stirring. The
resulting solution was stirred at room temperature while the course
of the reaction was monitored by TLC (CH2Cl2:CH3OH = 9:1). TLC
showed that the reaction was completed after 5 h. At this point, the
solution was washed with distilled water and brine. The organic
solution was dried over anhydrous Na2SO4, filtered and concentrat-
ed under reduced pressure. The product was purified by column
chromatography (CH2Cl2:CH3OH:Et3N = 20:1:trace).
ꢁ63.85 (m, 12F), ꢁ82.02 (t, J = 13.8 Hz, 6F), ꢁ106.80 to ꢁ107.20
(m, 4F), ꢁ124.00 to ꢁ124.30 (m, 4F); 13C NMR (CD3OD, 100 MHz)
d
: 33.2, 35.1, 50.8, 63.6, 69.1, 110–125, 128.4, 128.4, 128.9, 133.1,
134.6, 135.0, 136.6, 143.5, 169.6; IR (cmꢁ1): 3424.8, 3035.7, 1655.7,
1546.5, 1504.3, 1484.4; LRMS (MALDI) m/z 748.1 (M-2Cl-
CH2CH2NHCOC6H4CH2C6F13), 479.8 (C6F13CH2C6H4CONHCH2CH2);
HRMS
(MALDI)
calcd
for
C34H35F13N3O
(M-2Cl-
CH2CH2NHCOC6H4CH2C6F13) 748.2562, found. 748.2567.
4.2.7. Synthesis of ethanaminium, N-(carboxymethyl)-N,N-dimethyl-
2-[4-(3,3,4,4,5,5,5-heptafluoro-2,2-bis-trifluoromethyl-pentyl)-
benzoylamino]-, chloride, sodium salt (1:1:1) (7, FAS)
4: white solid, 5.126 g (89% yield); 1H NMR (DMSO-d6,
Compound 4 (1.151 g, 2.2 mmol, 1.1 equiv), ClCH2COONa
300 MHz)
d
:
2.16 (s, N(CH3)2, 6H), 2.38 (t, J = 6.6 Hz,
(0.232 g, 2.0 mmol, 1.0 equiv) and MeCN (20.0 mL) were placed
in a sealed glass tube and refluxed for 2 days with stirring under
argon atmosphere. Then the mixture was cooled to room
temperature and filtered. The solid was washed twice with
CH2Cl2, then dissolved in MeOH. Again the MeOH solution was
filtered and the filtrate was concentrated in vacuo leaving a white
solid. The solid was washed with acetone and dried giving a white
powder.
CH2CH2N(CH3)2, 2H), 3.34 (m, CH2CH2N(CH3)2, 2H), 3.80 (s,
C6F13CH2C6H4, 2H), 7.41 (d, J = 8.1 Hz, Ar-H, 2H), 7.80 (d,
J = 8.1 Hz, Ar-H, 2H), 8.44 (t, J = 5.4 Hz, NH, 1H); 19F NMR (CDCl3,
282 MHz)
d
: ꢁ62.56 to ꢁ62.76 (m, 6F), ꢁ80.41 (t, J = 13.7 Hz, 3F),
ꢁ106.15 to ꢁ106.55 (m, 2F), ꢁ123.25 to ꢁ123.60 (m, 2F); 13C NMR
(DMSO-d6, 100 MHz) d: 31.3, 37.4, 45.2, 58.1, 126.9, 131.5, 133.7,
134.3, 165.5; IR (cmꢁ1): 3269.3, 1629.5; LRMS (EI) m/z (%): 58
(100), 523 (0.4); HRMS (EI) calcd for C18H16F13N2O 523.1055,
found 523.1056.
7: white powder, 1.024 g (80% yield). 1H NMR (CD3OD,
300 MHz)
d: 3.33 (s, N(CH3)2, 6H), 3.76 (s, CH2COONa, 2H),
3.80–3.90 (m, NHCH2CH2N(CH3)2CH2COONa, 4H), 3.92 (s,
C6F13CH2C6H4, 2H), 7.46 (d, J = 7.8 Hz, Ar-H, 2H), 7.83 (d,
4.2.5. Synthesis of ethyl-{2-[4-(3,3,4,4,5,5,5-heptafluoro-2,2-bis-
trifluoromethyl-pentyl)-benzoylamino]-ethyl}-dimethyl-ammonium
iodide (5, FCS)
J = 7.8 Hz, Ar-H, 2H); 19F NMR (CD3OD, 282 MHz)
d
: ꢁ63.60 to
ꢁ63.90 (m, 6F), ꢁ82.04 (t, J = 14.0 Hz, 3F), ꢁ106.90 to ꢁ107.20 (m,
Compound 4 (0.646 g, 1.2 mmol, 1.0 equiv) and iodoethane
(0.374 g, 2.4 mmol, 2.0 equiv) were refluxed in MeCN (7.0 mL)
under argon atmosphere. The course of the reaction was monitored
by TLC (CH2Cl2:CH3OH = 24:1). TLC showed that the reaction was
completed after 3 h. Then the mixture was cooled to room
temperature. After the solution was evaporated under reduced
pressure, the residue was washed with acetone. The resulting
white solid was dried under reduced pressure.
2F), ꢁ124.10 to ꢁ124.40 (m, 2F); 13C NMR (CD3OD, 100 MHz)
d:
33.2, 35.2, 52.3, 62.8, 63.4, 65.5, 128.4, 133.1, 134.8, 136.5, 168.8,
169.7; IR (cmꢁ1): 3197.0, 3028.4, 2919.2, 1654.2, 1625.5, 1545.1,
1449.7; LRMS (MALDI) m/z 605.0 (MꢁCl). HRMS (MALDI) calcd for
C20H19F13N2O3Na (MꢁCl) 605.1080, found 605.1072.
Supporting information
5: white solid, 0.812 g (99% yield); 1H NMR (DMSO-d6,
1H NMR, 19F NMR and 13C NMR for the novel branched
fluorinated cationic (FCS), gemini (FGS), amphoteric (FAS) surfac-
tants and all the intermediates are provided.
300 MHz)
d: 1.27 (t, J = 6.3 Hz, N(CH3)2CH2CH3, 3H), 3.09 (s,
N(CH3)2, 6H), 3.38–3.50 (m, NHCH2CH2N(CH3)2CH2CH3, 4H), 3.60–
3.70 (m, CH2CH2N(CH3)2, 2H), 3.81 (s, C6F13CH2C6H4, 2H), 7.45 (d,
J = 8.1 Hz, Ar-H, 2H), 7.82 (d, J = 8.1 Hz, Ar-H, 2H), 8.82 (t, J = 5.0 Hz,
NH, 1H); 19F NMR (DMSO-d6, 282 MHz)
d
: ꢁ62.00 to ꢁ62.22 (m,
Acknowledgements
6F), ꢁ80.09 (t, J = 13.3 Hz, 3F), ꢁ105.90 to ꢁ106.40 (m, 2F),
ꢁ122.90 to ꢁ123.10 (m, 2F); 13C NMR (CD3OD, 100 MHz)
d: 8.7,
This work was supported by the National Basic Research
Program of China (973-2010CB833200 and 973-2010CB833300),
the National Natural Science Foundation of China (21102167), the
Science and Technology Commission of Shanghai Municipality
(12DZ1930902), Shanghai Green Chemical Engineering Technolo-
gy Research Center and the Knowledge Innovation Program of the
Chinese Academy of Sciences. We also thank Institute of Process
Engineering, Chinese Academy of Sciences for helping us doing the
surface tension measurements.
33.2, 34.9, 51.5, 61.5, 62.5, 128.3, 133.1, 134.6, 136.6, 169.6; IR
(cmꢁ1): 3279.5, 3202.2, 1650.7, 1455.2; LRMS (MALDI) m/z 553.1
(MꢁI); HRMS (MALDI) calcd for C20H22F13N2O (MꢁI) 553.1519,
found 553.1510.
4.2.6. Synthesis of [1,10-biphenyl]-4,40-dimethanaminium,
0
0
0
N4,N4,N4 ,N4 -tetramethyl-N4,N4 -bis-{2-[4-(3,3,4,4,5,5,5-
heptafluoro-2,2-bis-trifluoromethyl-pentyl)-benzoylamino]-ethyl}-,
chloride (1:2) (6, FGS)
Compound 4 (1.569 g, 3.0 mmol, 3.0 equiv) and 4,40-bis(chlor-
omethyl)-1,10-biphenyl (0.251 g, 1.0 mmol, 1.0 equiv) were
refluxed in MeCN (3.0 mL) under argon atmosphere for 2 days.
Then the mixture was cooled to room temperature and filtered. The
solid was washed twice with CH2Cl2, then dissolved in MeOH.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the